EP1329309A1 - Multilayers of fluoropolymers with chlorinated polyvinylchloride - Google Patents
Multilayers of fluoropolymers with chlorinated polyvinylchloride Download PDFInfo
- Publication number
- EP1329309A1 EP1329309A1 EP20030000922 EP03000922A EP1329309A1 EP 1329309 A1 EP1329309 A1 EP 1329309A1 EP 20030000922 EP20030000922 EP 20030000922 EP 03000922 A EP03000922 A EP 03000922A EP 1329309 A1 EP1329309 A1 EP 1329309A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- polyamide
- poly
- multilayers
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31739—Nylon type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31739—Nylon type
- Y10T428/31743—Next to addition polymer from unsaturated monomer[s]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/3175—Next to addition polymer from unsaturated monomer[s]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- the present invention relates to multilayers (laminates) comprising at least one layer A) of fluoropolymer, one intermediate layer B) and one layer C) of chlorinated polyvinyl chloride (CPVC), characterized in having a complete adhesion among the layers, so that at the delamination tests the specimen breaks without the layer separation.
- Said multilayers show, besides a high adhesion among the layers, good mechanical properties, good flame resistance and, from the fluoropolymer layer A) side, good resistance to chemical agents.
- thermoprocessable fluoropolymers in particular of fluoropolymers comprising units deriving from vinylidenfluoride (VDF) show good mechanical properties, very good resistance to flame and to chemical agents. However, they are expensive and those sheets of high thickness.
- VDF vinylidenfluoride
- the non-fluoro polymer layer must be of lower cost and flame resistance for preserving the performance of the all-fluoropolymer sheet.
- a good candidate is the CPVC which is not a very expensive thermoprocessable polymer and shows a good flame-resistance. It contains from 58% to 75% by weight of chlorine and is obtained by polyvinylchloride (PVC) chlorination.
- the Applicant has found that a bilayer of the aforesaid fluoropolymers with CPVC, obtained for example by applying a pressure on the overlapped layers maintained at their softening temperature, the adhesion is not obtained.
- An object of the present invention is therefore a multilayer comprising at least one laminate formed in sequence by the following layers:
- the sheet formed by A/B/C layers shows good mechanical and flame-resistance and has excellent resistance to chemical agents on the fluoropolymer side.
- the layer A) fluoropolymers of the present invention preferably contain at least 10% by moles of units derived from VDF.
- Said fluoropolymers can be VDF homopolymers or VDF copolymers with other ethylenically unsaturated monomers, preferably selected from the group formed by hexafluoropropene (HFP), chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE), perfluoroalkylvinylethers such for example perfluoropropylvinylether, trifluoroethylene, fluorodioxoles described in USP 6,201,084, ethylene, propylene.
- HFP hexafluoropropene
- CTFE chlorotrifluoroethylene
- TFE tetrafluoroethylene
- perfluoroalkylvinylethers such for example perfluoropropylvinylether, trifluoroethylene, fluorodioxoles described
- the comonomers copolymerized with VDF are in amounts such to obtain a thermoprocessable polymer.
- Said polymers are partially crystalline.
- PVDF polyvinylidenfluoride
- any polyamide can be used provided that it is blended with 0.01%-5% by weight of a diamine.
- the layer B) polyamides having an amount of -NH 2 end groups higher than 20 ⁇ eq/g can be prepared according to known methods, for example according to USP 4,543,378, wherein a chain transfer agent such, for example, m- or p-xylylendiamine, hexamethylendiamine or dodecamethylendiamine is used in the polymerization phase.
- a chain transfer agent such, for example, m- or p-xylylendiamine, hexamethylendiamine or dodecamethylendiamine is used in the polymerization phase.
- the layer B) polyamide having an amount of -NH 2 end groups higher than 20 ⁇ eq/g can also be obtained by mixing polyamides having a different -NH 2 end group content so that the final mixture contains an amount of -NH 2 end groups higher than 20 ⁇ eq/g.
- the layer B) polyamides can be of the (co)polyamide type such, for example, polyamide 6 (PA 6), polyamide 66 (PA 66), polyamide 11 (PA 11), polyamide 12 (PA 12).
- diamines these can be for example: protected amines, as hexamethylendiaminecarbamate and N,N'-dicinnamyilidene-1,6 hexandiamine; C 4 -C 20 aliphatic diamines such, for example, dodecyldiamine and decyldiamine; aromatic diamines such, for example, para-xylylendiamine.
- protected amines as hexamethylendiaminecarbamate and N,N'-dicinnamyilidene-1,6 hexandiamine
- C 4 -C 20 aliphatic diamines such, for example, dodecyldiamine and decyldiamine
- aromatic diamines such, for example, para-xylylendiamine.
- Protected diamines both aliphatic and aromatic, are preferred.
- the layer B) polymers preferably contain at least 10% by moles of monomers containing (-COO-) units and/or -CN groups.
- Said polymers can be poly(alkyl(meth)acrylates), for example poly(methylmethacrylate) (PMMA), or copolymers of alkyl(meth)-acrylates with acrylic acid, for example, poly(ethyl acrylate/acrylic acid), poly(ethylhexylacrylate/acrylic acid), poly(vinylesters), for example poly(vinylacetates), poly(acrylonitrile).
- PMMA poly(methylmethacrylate)
- copolymers of alkyl(meth)-acrylates with acrylic acid for example, poly(ethyl acrylate/acrylic acid), poly(ethylhexylacrylate/acrylic acid), poly(vinylesters), for example poly(vinylacetates), poly(acrylonitrile).
- polyalkyl(meth)acrylates in particular PMMA,
- polyamides having at least 20 ⁇ eq/g of NH 2 end groups or a polyamide blended with 0.01-5% by weight of a diamine, are used.
- the layer B) polyamides, having -NH 2 end groups higher than 20 ⁇ eq/g can optionally contain diamines.
- Layer B) can have a thickness much lower than that of layer C).
- Layer B) can also be formed by a blend of the polymer of layer A), or of layer C), optionally in admixture among each other, with at least 10% by weight, preferably at least 50% by weight of the layer B) polymer as above.
- the (co)polymers of the single layers of the invention can optionally contain additives such as fillers for example polytetrafluoroethylene (PTFE), silicates, graphite, titanium dioxide, lubricants, pigments, fire retardants, plasticizers, thermal and UV stabilizers.
- additives such as fillers for example polytetrafluoroethylene (PTFE), silicates, graphite, titanium dioxide, lubricants, pigments, fire retardants, plasticizers, thermal and UV stabilizers.
- the multilayer structures of the present invention can be obtained by co-extrusion.
- the single layers are laminated by compression at the polymer softening temperature.
- the multilayers according to the present invention can be used as structural elements for working plans, coating panels, in the building of moulded articles, for example "wet-benches", used in the semicon industry.
- the M.I. of the fluorinated polymers is measured according to the ASTM D 1238 method, at 232°C and with a load of 5 kg.
- the T mII of the fluorinated polymers is determined by differential scanning calorimetry (DSC).
- the Tg of the CPVC polymers is determined by differential scanning calorimetry (DSC).
- the number of the -NH 2 end groups of polyamides is determined by preparing a solution at 2% of polyamide in m-cresol and subsequent titration with perchloric acid.
- Polyamide 12 (PA 12) having -NH 2 end groups equal to 110 ⁇ eq/g
- Some films of the polyamide having a thickness of 0.3 mm have been obtained by compression moulding.
- Plaques having a thickness of 6 mm have been obtained by compression moulding from a CPVC polymer having Tg equal to 112°C and chlorine content equal to 64.24% by weight.
- the single layers A), B) and C), previously obtained, have been overlapped and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- the plaques of the single layers A) and C), previously obtained, have been overlapped and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- the A)/C) laminate does not show any adhesion between the layers.
- PA 12 having -NH 2 end groups equal to 13 ⁇ eq/g
- Some films of the polyamide having a thickness of 0.3 mm has been obtained by compression moulding.
- the single layers A), B) and C), previously obtained, have been overlapped and kept under pressure (about 2-3 bar), at a temperature of 200°C for 10 minutes.
- the A)/B)/C) laminate does not show any adhesion among the layers.
- Polyamide PA 12 with -NH 2 end groups equal to 13 ⁇ eq/g blended with 1% by weight of diamine
- the single layers A), B) and C), previously obtained, have been overlapped according to the sequence A)/B)/C)/B)/A) and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- the single layers A), B) and C), previously obtained, have been overlapped according to the sequence A)/B)/C)/B)/A) and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- Example 1 The polymer of Example 1 is used.
- a film having a thickness of 0.3 mm has been obtained from a polymethylmethacrylate by compression moulding.
- Example 1 The polymer of Example 1 is used.
- the single layers A), B) and C), previously obtained, have been overlapped and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- Example 6 The polymer of Example 6 is used.
- the single layers A), B) and C), previously obtained, have been overlapped according to the sequence A)/B)/C)/B)/A) and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- Plaques having a thickness of 1.5 mm have been obtained by compression moulding from a polymer formed by units of vinylidenfluroride (VDF), tetrafluororethylene (TFE) and hexafluoropropene (HFP) in a molar ratio 37/48/15, having T mII equal to 161.8°C.
- VDF vinylidenfluroride
- TFE tetrafluororethylene
- HFP hexafluoropropene
- Polyamide PA 12 having -NH 2 end groups equal to 32 ⁇ eq/g
- the single layers A), B) and C), previously obtained, have been overlapped and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- Films having a thickness of 0.3 mm have been prepared from the granules by compression moulding.
- the single layers A), B) and C), previously obtained, have been overlapped and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
Abstract
Description
- The present invention relates to multilayers (laminates) comprising at least one layer A) of fluoropolymer, one intermediate layer B) and one layer C) of chlorinated polyvinyl chloride (CPVC), characterized in having a complete adhesion among the layers, so that at the delamination tests the specimen breaks without the layer separation. Said multilayers show, besides a high adhesion among the layers, good mechanical properties, good flame resistance and, from the fluoropolymer layer A) side, good resistance to chemical agents.
- The sheets of thermoprocessable fluoropolymers, in particular of fluoropolymers comprising units deriving from vinylidenfluoride (VDF) show good mechanical properties, very good resistance to flame and to chemical agents. However, they are expensive and those sheets of high thickness.
- One way for producing less expensive sheets is to use the concept of laminates in which the fluoropolymer layer thickness is substantially reduced. Therefore, the non-fluoro polymer layer must be of lower cost and flame resistance for preserving the performance of the all-fluoropolymer sheet. A good candidate is the CPVC which is not a very expensive thermoprocessable polymer and shows a good flame-resistance. It contains from 58% to 75% by weight of chlorine and is obtained by polyvinylchloride (PVC) chlorination.
- The Applicant has found that a bilayer of the aforesaid fluoropolymers with CPVC, obtained for example by applying a pressure on the overlapped layers maintained at their softening temperature, the adhesion is not obtained.
- It has been surprisingly and unexpectedly found that it is possible to obtain an excellent adhesion between the fluoropolymers of layer A) and the CPVC of layer C) if a thin polymer layer as defined below is interposed between them.
- An object of the present invention is therefore a multilayer comprising at least one laminate formed in sequence by the following layers:
- A) one thermoprocessable fluoropolymer layer comprising units deriving from vinylidenfluoride (VDF) ;
- B) one polyamide layer blended with 0.01%-5% by weight of a diamine or one polyamide layer having at least 20 µeq/g of -NH2 groups, or one thermoprocessable polymer layer containing (-COO-) units and/or -CN groups; and
- C) one layer based on chlorinated polyvinylchloride (CPVC) containing from 58% to 75% by weight, preferably from 60% to 70% by weight of chlorine.
-
- The sheet formed by A/B/C layers shows good mechanical and flame-resistance and has excellent resistance to chemical agents on the fluoropolymer side.
- To obtain a sheet wherein both the external surfaces are resistant to chemical agents it is possible to prepare a multi layer with the following sequence of layers A/B/C/B/A.
- It is therefore a further object of the present invention a multi layer formed by five layers A/B/C/B/A wherein A, B and C have the above meaning.
- The layer A) fluoropolymers of the present invention preferably contain at least 10% by moles of units derived from VDF. Said fluoropolymers can be VDF homopolymers or VDF copolymers with other ethylenically unsaturated monomers, preferably selected from the group formed by hexafluoropropene (HFP), chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE), perfluoroalkylvinylethers such for example perfluoropropylvinylether, trifluoroethylene, fluorodioxoles described in USP 6,201,084, ethylene, propylene.
- The comonomers copolymerized with VDF are in amounts such to obtain a thermoprocessable polymer.
- Said polymers are partially crystalline.
- Preferably as layer A), polyvinylidenfluoride (PVDF) is used.
- In layer B) any polyamide can be used provided that it is blended with 0.01%-5% by weight of a diamine.
- The layer B) polyamides having an amount of -NH2 end groups higher than 20 µeq/g, can be prepared according to known methods, for example according to USP 4,543,378, wherein a chain transfer agent such, for example, m- or p-xylylendiamine, hexamethylendiamine or dodecamethylendiamine is used in the polymerization phase.
- The layer B) polyamide having an amount of -NH2 end groups higher than 20 µeq/g can also be obtained by mixing polyamides having a different -NH2 end group content so that the final mixture contains an amount of -NH2 end groups higher than 20 µeq/g.
- The layer B) polyamides can be of the (co)polyamide type such, for example, polyamide 6 (PA 6), polyamide 66 (PA 66), polyamide 11 (PA 11), polyamide 12 (PA 12).
- When layer B) polyamides are added with diamines, these can be for example: protected amines, as hexamethylendiaminecarbamate and N,N'-dicinnamyilidene-1,6 hexandiamine; C4-C20 aliphatic diamines such, for example, dodecyldiamine and decyldiamine; aromatic diamines such, for example, para-xylylendiamine. Protected diamines, both aliphatic and aromatic, are preferred.
- The layer B) polymers preferably contain at least 10% by moles of monomers containing (-COO-) units and/or -CN groups. Said polymers can be poly(alkyl(meth)acrylates), for example poly(methylmethacrylate) (PMMA), or copolymers of alkyl(meth)-acrylates with acrylic acid, for example, poly(ethyl acrylate/acrylic acid), poly(ethylhexylacrylate/acrylic acid), poly(vinylesters), for example poly(vinylacetates), poly(acrylonitrile). Among the layer B) polymers containing (-COO-) units, polyalkyl(meth)acrylates, in particular PMMA, are preferred.
- Preferably as layer B) polyamides having at least 20 µeq/g of NH2 end groups or a polyamide blended with 0.01-5% by weight of a diamine, are used.
- The layer B) polyamides, having -NH2 end groups higher than 20 µeq/g can optionally contain diamines. Layer B) can have a thickness much lower than that of layer C). Layer B) can also be formed by a blend of the polymer of layer A), or of layer C), optionally in admixture among each other, with at least 10% by weight, preferably at least 50% by weight of the layer B) polymer as above.
- The (co)polymers of the single layers of the invention can optionally contain additives such as fillers for example polytetrafluoroethylene (PTFE), silicates, graphite, titanium dioxide, lubricants, pigments, fire retardants, plasticizers, thermal and UV stabilizers.
- The multilayer structures of the present invention can be obtained by co-extrusion. Alternatively, the single layers are laminated by compression at the polymer softening temperature.
- The multilayers according to the present invention can be used as structural elements for working plans, coating panels, in the building of moulded articles, for example "wet-benches", used in the semicon industry.
- Some illustrative Examples follow which are not limitative of the present invention.
- The following characterizations carried out on the used polymers are indicated hereinafter:
- The M.I. of the fluorinated polymers is measured according to the ASTM D 1238 method, at 232°C and with a load of 5 kg.
- The TmII of the fluorinated polymers is determined by differential scanning calorimetry (DSC).
- The Tg of the CPVC polymers is determined by differential scanning calorimetry (DSC).
- It has been determined by elemental analysis.
- The number of the -NH2 end groups of polyamides is determined by preparing a solution at 2% of polyamide in m-cresol and subsequent titration with perchloric acid.
- From a PVDF polymer having a TmII equal to 167°C, and MI equal to 2 g/10', plaques having a thickness of 1.5 mm have been obtained by compression moulding.
- Some films of the polyamide having a thickness of 0.3 mm have been obtained by compression moulding.
- Plaques having a thickness of 6 mm have been obtained by compression moulding from a CPVC polymer having Tg equal to 112°C and chlorine content equal to 64.24% by weight.
- The single layers A), B) and C), previously obtained, have been overlapped and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- By applying a mechanical force one tries to separate layer A) from layer C).
- One cannot measure the adhesion force between layer A) and layer C). By increasing the force to separate the layers, one breaks the manufactured article without obtaining the delamination. This shows that the laminate according to the invention shows a high adhesion.
- The same polymer of Example 1 is used.
- The same polymer of Example 1 is used.
- The plaques of the single layers A) and C), previously obtained, have been overlapped and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- The A)/C) laminate does not show any adhesion between the layers.
- The same polymer of Example 1 is used.
- Some films of the polyamide having a thickness of 0.3 mm has been obtained by compression moulding.
- The same polymer of Example 1 is used.
- The single layers A), B) and C), previously obtained, have been overlapped and kept under pressure (about 2-3 bar), at a temperature of 200°C for 10 minutes.
- The A)/B)/C) laminate does not show any adhesion among the layers.
- The same polymer of Example 1 is used.
- One kilogram of PA 12 in granules, having -NH2 end groups equal to 13 µeq/g, has been blended with 1% by weight of hexamethylendiamine monocarbamate. Then it has been pelletized in a single screw Brabender extruder in Hastelloy C-276 having a diameter of 18 mm and a length equivalent to 25 times the diameter with a melt temperature of 225°C. Two films having a thickness of 0.3 mm have been obtained from the granules by compression moulding.
- The same polymer of Example 1 is used.
- The single layers A), B) and C), previously obtained, have been overlapped according to the sequence A)/B)/C)/B)/A) and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- By applying a mechanical force one tries to separate the layers.
- One cannot measure the adhesion force among the layers. By increasing the force to separate the layers, one breaks the manufactured article without obtaining the delamination. This shows that the laminate according to the invention shows a high adhesion.
- Example 4 is repeated wherein layer B) is a polyamide PA 12 having -NH2 end groups equal to 45 µeq/g obtained by mechanically mixing 330 g of PA 12 of Example 1 (-NH2 = 110 µeq/g) with 670 g of PA 12 of Example 2 (-NH2 = 13 µeq/g). Then the blend has been pelletized in a single screw Brabender extruder in Hastelloy C-276 having a diameter of 18 mm and a length equivalent to 25 times the diameter, with a melt temperature of 225°C. Two films having a thickness of 0.3 mm have been prepared from the granules by compression moulding.
- The single layers A), B) and C), previously obtained, have been overlapped according to the sequence A)/B)/C)/B)/A) and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- By applying a mechanical force one tries to separate the layers.
- One cannot measure the adhesion force among the layers. By increasing the force to separate the layers, one breaks the manufactured article without obtaining the delamination. This shows that the laminate according to the invention shows a high adhesion.
- The polymer of Example 1 is used.
- A film having a thickness of 0.3 mm has been obtained from a polymethylmethacrylate by compression moulding.
- The polymer of Example 1 is used.
- The single layers A), B) and C), previously obtained, have been overlapped and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- By applying a mechanical force one tries to separate layer A) from layer C).
- One cannot measure the adhesion force between layer A) and layer C). By increasing the force to separate the layers, one breaks the manufactured article without obtaining the delamination. This shows that the laminate according to the invention shows a high adhesion.
- The same polymer of Example 1 is used.
- The polymer of Example 6 is used.
- The same polymer of Example 1 is used.
- The single layers A), B) and C), previously obtained, have been overlapped according to the sequence A)/B)/C)/B)/A) and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- By applying a mechanical force one tries to separate the layers.
- One cannot measure the adhesion force among the layers. By increasing the force to separate the layers, one breaks the manufactured article without obtaining the delamination. This shows that the laminate according to the invention shows a high adhesion.
- Plaques having a thickness of 1.5 mm have been obtained by compression moulding from a polymer formed by units of vinylidenfluroride (VDF), tetrafluororethylene (TFE) and hexafluoropropene (HFP) in a molar ratio 37/48/15, having TmII equal to 161.8°C.
- The polyamide has been obtained by mechanically mixing 200 g of PA 12 of Example 1 (-NH2 = 110 µeq/g) with 800 g of PA 12 of Example 2 (-NH2 = 13 µeq/g). Then the blend has been pelletized in a single screw Brabender extruder in Hastelloy C-276 having a diameter of 18 mm and a length equivalent to 25 times the diameter, with a melt temperature of 225°C. Films having a thickness of 0.3 mm have been prepared from the granules by compression moulding.
- The same polymer of Example 1 is used.
- The single layers A), B) and C), previously obtained, have been overlapped and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- By applying a mechanical force one tries to separate layer A) from layer C).
- One cannot measure the adhesion force between layer A) and layer C). By increasing the force to separate the layers, one breaks the manufactured article without obtaining the delamination. This shows that the laminate according to the invention shows a high adhesion.
- The same polymer of Example 1 is used.
- Films having a thickness of 0.3 mm have been prepared from the granules by compression moulding.
- The same polymer of Example 1 is used.
- The single layers A), B) and C), previously obtained, have been overlapped and kept under pressure (about 2-3 bar) at a temperature of 200°C for 10 minutes.
- By applying a mechanical force one tries to separate layer A) from layer C).
- One cannot measure the adhesion force between layer A) and layer C). By increasing the force to separate the la-yers, one breaks the manufactured article without obtaining the delamination. This shows that the laminate according to the invention shows a high adhesion.
Claims (11)
- Multilayers comprising at least one laminate formed in sequence by the following layers:A) one thermoprocessable fluoropolymer layer comprising units deriving from vinylidenfluoride (VDF);B) one polyamide layer blended with 0.01%-5% by weight of a diamine or one polyamide layer having at least 20 µeq/g of -NH2 groups, or one thermoprocessable polymer layer containing (-COO-) units and/or -CN groups; andC) one layer based on chlorinated polyvinylchloride (CPVC) containing from 58% to 75% by weight, preferably from 60% to 70% by weight of chlorine.
- Multilayers according to claim 1, wherein layer B) is formed by a blend of the polymer of layer A) or of layer C), optionally in admixture among each other, with at least 10% by weight, preferably at least 50% by weight, of layer B) polymer.
- Multilayers according to claims 1-2, formed in sequence by five layers A)/B)/C)/B)/A).
- Multilayers according to claims 1-3, wherein layer A) fluoropolymers contain at least 10% by moles of units derived from VDF.
- Multilayers according to claims 1-4, wherein layer A) fluoropolymers are VDF homopolymers or VDF copolymers with monomers selected from the group formed by hexafluoropropene (HFP), chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE), perfluoroalkylvinylethers, trifluoroethylene, fluorodioxoles, ethylene, propylene.
- Multilayers according to claims 1-5, wherein layer A) fluoropolymer is polyvinylidenfluoride (PVDF).
- Multilayers according to claims 1-6, wherein layer B) polyamides are (co)polyamides selected from the group formed by polyamide 6 (PA 6), polyamide 66 (PA 66), polyamide 11 (PA 11), polyamide 12 (PA 12).
- Multilayers according to claims 1-7, wherein the diamines blended with layer B) polyamides are selected from the group formed by hexamethylendiaminecarbamate and N,N'-dicinnamylidene-1,6 hexandiamine; C4-C20 aliphatic diamines, preferably dodecyldiamine and decyldiamine; aromatic diamines, preferably para-xylylendiamine.
- Multilayers according to claims 1-8, wherein layer B) is formed by poly(alkyl(meth)acrylates) , preferably poly(methylmethacrylate) (PMMA), or copolymers of alkyl(meth)acrylates with acrylic acid, for example, poly(ethyl acrylate/acrylic acid), poly(ethylhexylacrylate/acrylic acid), poly(vinylesters), for example poly(vinylacetates), poly(acrylonitrile).
- Multilayers according to claims 1-9, wherein layer B) thermoprocessable polymers contain at least 10% by moles of monomers containing (-COO-) units and/or -CN groups.
- Moulded articles, preferably "wet-benches" obtainable from the multilayers according to claims 1-9.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI20020101 | 2002-01-22 | ||
IT2002MI000101A ITMI20020101A1 (en) | 2002-01-22 | 2002-01-22 | COUPLED OF FLUOROPOLYMERS WITH CHLORINATED POLYVINYL CHLORIDE |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1329309A1 true EP1329309A1 (en) | 2003-07-23 |
EP1329309B1 EP1329309B1 (en) | 2006-10-04 |
Family
ID=11448938
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03000922A Expired - Fee Related EP1329309B1 (en) | 2002-01-22 | 2003-01-16 | Multilayers of fluoropolymers with chlorinated polyvinylchloride |
Country Status (6)
Country | Link |
---|---|
US (2) | US7033671B2 (en) |
EP (1) | EP1329309B1 (en) |
JP (1) | JP4386648B2 (en) |
CA (1) | CA2416716A1 (en) |
DE (1) | DE60308736T2 (en) |
IT (1) | ITMI20020101A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2900094A1 (en) * | 2006-04-19 | 2007-10-26 | Arkema Sa | MULTI-LAYER STRUCTURE BASED ON FLUORINE POLYMER AND PVC |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105339164B (en) * | 2013-03-14 | 2019-03-12 | 施内勒公司 | The flexible touch laminated material with improved flame-retarding characteristic for transport |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2177412A1 (en) * | 1995-06-06 | 1996-12-07 | Anthony W. Brant | Thermoplastic blend material for capping or coating composite |
US5700578A (en) * | 1995-06-26 | 1997-12-23 | Crane Plastics Company Limited Partnership | Fluoropolymer/terpolymer composite |
EP1101994A2 (en) * | 1999-11-16 | 2001-05-23 | Tokai Rubber Industries, Ltd. | Fuel hose |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US453378A (en) * | 1891-06-02 | Cable-clamping device | ||
FR2239501B1 (en) * | 1973-07-10 | 1976-06-18 | Solvay | |
IT1119928B (en) * | 1978-09-25 | 1986-03-19 | Ugine Kuhlmann | COMPOSITE MATERIAL OF VINYLIDENE POLYFLUORIDE AND INCOMPATIBLE THERMOPLASTIC POLYMER AND PROCEDURE FOR ITS MANUFACTURE |
JPS6030706B2 (en) | 1982-07-21 | 1985-07-18 | 宇部興産株式会社 | polyamide composition |
WO1995009081A1 (en) * | 1993-09-28 | 1995-04-06 | Ems-Inventa Ag | Multiply polymer pipe |
US5658670A (en) * | 1994-08-19 | 1997-08-19 | Minnesota Mining And Manufactury Company | Multi-layer compositions having a fluoropolymer layer |
IT1288121B1 (en) * | 1996-07-01 | 1998-09-10 | Ausimont Spa | THERMOPLASTIC COPOLYMERS OF VINYLIDENFLUORIDE (VDF) |
US6432542B1 (en) * | 1997-11-06 | 2002-08-13 | Alliedsignal Inc. | Multicomponent structures having improved adhesion |
-
2002
- 2002-01-22 IT IT2002MI000101A patent/ITMI20020101A1/en unknown
-
2003
- 2003-01-16 DE DE60308736T patent/DE60308736T2/en not_active Expired - Lifetime
- 2003-01-16 EP EP03000922A patent/EP1329309B1/en not_active Expired - Fee Related
- 2003-01-20 CA CA002416716A patent/CA2416716A1/en not_active Abandoned
- 2003-01-20 JP JP2003010922A patent/JP4386648B2/en not_active Expired - Fee Related
- 2003-01-21 US US10/347,353 patent/US7033671B2/en not_active Expired - Fee Related
-
2006
- 2006-02-21 US US11/357,030 patent/US7282267B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2177412A1 (en) * | 1995-06-06 | 1996-12-07 | Anthony W. Brant | Thermoplastic blend material for capping or coating composite |
US5700578A (en) * | 1995-06-26 | 1997-12-23 | Crane Plastics Company Limited Partnership | Fluoropolymer/terpolymer composite |
EP1101994A2 (en) * | 1999-11-16 | 2001-05-23 | Tokai Rubber Industries, Ltd. | Fuel hose |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2900094A1 (en) * | 2006-04-19 | 2007-10-26 | Arkema Sa | MULTI-LAYER STRUCTURE BASED ON FLUORINE POLYMER AND PVC |
WO2007122335A1 (en) * | 2006-04-19 | 2007-11-01 | Arkema France | Multi-layer structure based on fluoride polymer functionalised by irradiation and pvc |
Also Published As
Publication number | Publication date |
---|---|
US20060141263A1 (en) | 2006-06-29 |
US7282267B2 (en) | 2007-10-16 |
CA2416716A1 (en) | 2003-07-22 |
ITMI20020101A0 (en) | 2002-01-22 |
DE60308736T2 (en) | 2007-08-23 |
DE60308736D1 (en) | 2006-11-16 |
JP2003320626A (en) | 2003-11-11 |
US7033671B2 (en) | 2006-04-25 |
ITMI20020101A1 (en) | 2003-07-22 |
EP1329309B1 (en) | 2006-10-04 |
US20030138636A1 (en) | 2003-07-24 |
JP4386648B2 (en) | 2009-12-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6849314B2 (en) | Fluoropolymer blends and multilayer articles | |
US6489420B1 (en) | Fluoropolymers with improved characteristics | |
US6197393B1 (en) | Multi-layer compositions comprising a fluoropolymer | |
US6790912B2 (en) | Extrudable fluoropolymer blends | |
US7569275B2 (en) | Fluoropolymer articles | |
US9056974B2 (en) | Fluoropolymer modified acrylic capstock | |
WO1998008879A1 (en) | Method of improving adhesion between a fluoropolymer and a hydrocarbon substrate | |
JP5065559B2 (en) | Multilayer composition comprising a fluoropolymer and a hydrogenated polymer | |
JP2005526641A (en) | Fluoropolymer-perfluoropolymer laminate | |
US7282267B2 (en) | Multilayers of fluoropolymers with chlorinated polyvinylchloride | |
JP4959911B2 (en) | Fluororesin film and laminate containing layer of the film | |
US6878453B2 (en) | Multilayers of polyamides and CPVC | |
US20190284451A1 (en) | Self-priming adhesive | |
JP2505327B2 (en) | Laminated material containing soft fluororesin | |
JPH06255050A (en) | Transport resin laminated body | |
CN109312141A (en) | Self-priming adhesive |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO |
|
17P | Request for examination filed |
Effective date: 20040107 |
|
AKX | Designation fees paid |
Designated state(s): DE FR GB IT |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB IT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20061004 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 60308736 Country of ref document: DE Date of ref document: 20061116 Kind code of ref document: P |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20070705 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20151208 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20160127 Year of fee payment: 14 Ref country code: DE Payment date: 20160112 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20160113 Year of fee payment: 14 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60308736 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20170116 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20170929 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170801 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170116 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170116 |